KR102362954B1 - Solid-liquid crude oil compositions and fractionation processes thereof - Google Patents

Abstract

A method of making a fractionated product is disclosed, comprising providing a solid hydrocarbonaceous material wherein the material is in particulate form and wherein at least about 90% by volume (%v) of the particles have a diameter of about 500 μm or less. The solid hydrocarbonaceous material is mixed with an unrefined liquid hydrocarbonaceous material such as crude oil to produce a mixed solid-liquid blend; The mixed solid-liquid blend is fractionated to produce one or more fractionation products. Typically the solid hydrocarbonaceous material comprises coal, optionally the coal is ultrafine coal and suitably the coal comprises fine coal. The coal may be dewatered and deashed prior to mixing with the crude liquid hydrocarbonaceous material. Further provided are compositions and products of the process.

Description

SOLID-LIQUID CRUDE OIL COMPOSITIONS AND FRACTIONATION PROCESSES THEREOF

The present invention is in the field of mixing products derived from liquid hydrocarbons and solids, in particular crude oil and coal, to produce a mixed product, which may be subjected to further refining and processing. In particular, the present invention is in the field of introducing solid hydrocarbons, such as coal, into crude oil refining processes to upgrade solid hydrocarbons and replace some of the crude oil in refinery streams.

Coal fines and ultrafines, including microfines, are small particles of coal produced from large coal masses during mining and manufacturing processes. Coal pulverization has the same energy potential as coal, but is generally considered a waste because the particulate nature of the product makes it difficult to market and transport. Coal pulverization thus forms large waste heaps or large waste piles that require careful future management to avoid environmental pollution or even threats to human life, as evidenced by the 1966 Aberfan disaster in South Wales, England. Soil near coal mines contained within ponds, usually discarded.

Nevertheless, coal pulverization provides an inexpensive and abundant supply of hydrocarbons, particularly carbon-rich. It is known to add a slurry of coal fines in water to fuel oils to upgrade the coal fines product and reduce the cost per unit volume of the blended fuel oil (see for example US5096461, US5902359 and US4239426). However, in their natural state, coal fines typically contain significant levels of ash-forming components that can render them unsuitable for blending with crude oil. Moreover, the amount of water present in the coal fines (about 35% by mass or %m) is also undesirable for use in crude oil. In addition, although the sulfur content of coal fines is similar to crude oil, a means of reducing sulfur in coal for use with crude oil is desirable because low sulfur containing crudes are more valuable than high sulfur containing crudes. Selecting coal fines with a low mineral matter content is one of the possibilities for ameliorating this problem, grinding seam coals that are selected to have an inherently low mineral content (eg <5% m) and It can be produced by grinding, but this practically limits the types of coal available.

Crude oil is classified as a fossil fuel and is a non-renewable energy source. Moreover, although oil prices fluctuate considerably, refined products obtained from crude oil are always significantly more expensive. A way in which crude oil can be blended with low-cost waste such as coal pulverization to increase the limited reserves of crude oil, and the resulting refined distillate product, would be highly desirable.

These and other uses, features and advantages of the present invention should be apparent to those skilled in the art from the teachings provided herein.

US5503646 refers to solid-liquid extraction of crude-coal mixtures with an emphasis on upgraded coal products, and is specialized for lower grade coals (lignite and sub-bituminous coal). US5503646 uses a solid-liquid extraction technique to separate crude coal particles (150-250 microns (μm)) and a solid product from a heated slurry. US5503646 does not use distillation.

US5096461, US5902359, US4239426 and US 4309269 all refer to processes for mixtures of water as well as coal and crude oil to enable coal pipeline transport. US4309269 refers to the dissolution of coal in a crude-coal slurry, albeit under high pressure.

US4900429 describes a process for producing synthetic crude oil by hydrocracking heavy oil, pulverized coal and pyrolyzed coal volatiles.

JPS54129008, JPS5636589 and JPS5798595 refer to stable dispersions of crude oil and pulverised coal (particle size 50-100 μm) using surfactants. JP2000290673 and US7431744 refer to methods of increasing the calorific value of coal by adding crude oil as a slurry or briquette.

Curtis, C. W. et al. (Evaluation of process parameter for combined processing of coal with heavy crudes and residua (Ind. Eng. Chem. Process Des. Dev., 1985, 24, 1259)) found that coal and petroleum crude oil/ It deals with the co-treatment of the residue, but uses catalysts and requirements for hydrogen under pressure. The fraction was solvent extracted and not distilled. CN105567321 and CN101649220 provide another variant of coal liquefaction technology that uses crude oil as the liquefaction solvent, but requires a catalytic high pressure hydrogenation unit. The resulting product was an undistilled extracted solvent. This process is energy intensive and relies on the presence of a hydrogen atmosphere and catalyst that severely lowers the conversion of coal to upgraded products in low yields that otherwise would not be commercially feasible.

British Coal Corporation, CEC report EUR 18247 (Improvements on direct coal liquefaction, 1999, ISBN 92-828-5444-2) mentions direct liquefaction of coal by co-refining with hydrogenated anthracene oil solvent do.

Bartle, K. E. and Taylor, N. CEC report EUR 13168 (Co-refining of Coal and Petroleum, 1991, ISBN 92-826-2220-7) of Co-refining of Coal by Co-Refining with Heavy Petroleum-derived Fractions under One Step Catalytic Hydro-liquefaction Conditions. Direct liquefaction is mentioned.

The present invention not only changes or expands the range of valuable fractions obtainable from crude hydrocarbonaceous substrates, but also reduces dependence on crude oil as a source of valuable petrochemicals, but solves the problems existing in the prior art .

Accordingly, in a first aspect of the present invention there is provided a method for preparing a fractionated product comprising the steps of: (i) providing a solid hydrocarbonaceous material, wherein the material is in particulate form , wherein at least about 90% by volume (%v) of the particles have a diameter of about 500 μm or less;

(ii) mixing the solid hydrocarbonaceous material with the crude liquid hydrocarbonaceous material to produce a mixed solid-liquid blend;

(iii) fractionation is performed on the mixed solid-liquid blend to produce one or more fractionation products.

Typically the solid hydrocarbonaceous material comprises coal, optionally the coal is ultrafine coal, suitably the coal comprises microfine coal. Where the coal is ultrafine coal, typically at least 95% by volume (%v), optionally 98%v, suitably 99%v, of the particles have a diameter of about 500 μm or less. In one embodiment of the present invention, the ultrafine coal typically comprises particles having at least 95%v, optionally 98%v, suitably 99%v of the particles having a diameter of about 250 μm or less.

In certain embodiments of the present invention coal typically has at least 95%v, optionally 98%v, suitably 99%v of the particles having a diameter of about 100 μm or less, optionally about 50 μm, and more optionally It contains fine coals with particles that are about 20 μm. In a still further embodiment at least 95% v of the particles have a diameter of less than 10 μm.

According to one embodiment of the invention the solid hydrocarbonaceous material is subjected to at least one dehydration step prior to step (i).

According to another embodiment of the invention the solid hydrocarbonaceous material is subjected to at least one ash removal (eg demineralization) step prior to step (i).

In certain embodiments of the present invention the solid hydrocarbonaceous material comprises coal selected due to its low intrinsic ash content. In an embodiment the coal has an intrinsic ash content of less than 20% by mass (%m), suitably less than 10%m, optionally less than 5%m.

In certain embodiments of the present invention, the crude liquid hydrocarbonaceous material comprises or consists essentially of crude oil. Suitably the crude oil is a sweet crude oil. Optionally, the crude oil is sour crude oil.

In yet a further embodiment of the present invention the solid hydrocarbonaceous material is a mixed solid-liquid comprising up to about 60% m (60% by mass) of solid hydrocarbonaceous material, based on the total mass of the mixed solid-liquid blend. It is mixed with a liquid hydrocarbonaceous material to create a blend. Suitably, the mixed solid-liquid blend has at most about 40% m, optionally at most about 30% m, typically at most about 20% m of solid hydrocarbonaceous, based on the total mass of the mixed solid-liquid blend. contains substances. Suitably, the mixed solid-liquid blend has at least about 0.01% m, optionally at least about 0.1% m, typically at least about 1% m of solid hydrocarbonaceous, based on the total mass of the mixed solid-liquid blend. contains substances. In certain embodiments of the present invention, the mixed solid-liquid blend comprises at least about 10% m of solid hydrocarbonaceous material, based on the total mass of the mixed solid-liquid blend.

In one embodiment of the invention, fractionation comprises distillation at or near atmospheric pressure. Optionally, the distillation is carried out under reduced pressure. In an embodiment of the invention, fractionation by distillation takes place under atmospheric pressure and then under reduced pressure.

According to an embodiment of the present invention, the at least one fractionated product of the process comprises a distillate product obtained from both solid hydrocarbonaceous material and crude liquid hydrocarbonaceous material. Suitably the bottoms distillate product is gasoline; naphtha; kerosene; and at least one selected from the group consisting of diesel.

Certain embodiments of the present invention provide at least one fractionated product of a process comprising a middle distillate product derived from both solid hydrocarbonaceous material and crude liquid hydrocarbonaceous material. Suitably the middle distillate product comprises at least one of the group selected from: marine diesel; light vacuum gas oil; and heavy vacuum gas oil. In yet a further embodiment the present invention provides at least one fractionated product of a process comprising vacuum residues derived from both solid hydrocarbonaceous material and crude liquid hydrocarbonaceous material. Suitably the vacuum residue comprises asphalt and/or bitumen.

In certain embodiments of the present invention the mixed solid-liquid blend product further comprises a dispersant additive.

In yet another further embodiment of the invention, the method comprises at least 1%v, suitably at least 2%v and optionally at least 3% v as determined compared to an equivalent solid-liquid blend in which the solid particulate material is inert. gives an increase in the total distillate fraction of v.

A second aspect of the present invention provides a fractionated product obtainable or obtained by the process described herein.

A third aspect of the present invention provides a method of operating a fractionator comprising the steps of:

mixing the coal pulverized material, wherein the material is in particulate form and has a diameter of about 500 μm or less to produce a solid-liquid blend in which at least about 95%v of the particles are mixed with crude oil;

the blended solid-liquid blend comprises at least about 0.01% m and up to about 60% m of coal pulverulent material, based on the total mass of the blended solid-liquid blend;

introducing the mixed solid-liquid blend to a fractionation column or mixing crude oil and coal pulverized material in situ in the fractionation column at or near atmospheric pressure; and

raising the temperature of the fractionation column to effect fractionation of the mixed solid-liquid blend to produce one or more fractionation products.

In a further embodiment the one or more fractionation products are further fractionated under reduced pressure to produce one or more reduced pressure (eg vacuum) fractionation products.

A fourth aspect of the present invention provides a mixed solid-liquid blend product comprising a dewatered ultrafine coal preparation with crude oil, wherein the dewatered ultrafine coal is at least 95% of the particles, optionally, optionally 98%, suitably 99%, are characterized as having a diameter of about 500 μm or less, the solid-liquid blend comprising up to about 60% m of dewatered ultrafine coal based on the total mass of the blended solid-liquid blend .

In one embodiment of the invention, the blended solid-liquid blend product typically comprises ultrafine coal comprising at least 95%, optionally 98%, suitably 99% of the particles having a diameter of about 250 μm or less. include

In certain embodiments of the invention the dewatered ultrafine coal typically has at least 95%, optionally 98%, suitably 99% of the particles having a diameter of about 100 μm or less, optionally about 50 μm, and more optionally about It contains fine coal containing particles of 20 μm.

The ultra pulverized coal dewatered in accordance with certain embodiments of the present invention comprises a low intrinsic ash content. Suitably the ash content is less than about 20% m of ultrafine coal based on the total mass of the blended solid-liquid blend; optionally less than about 15% m, suitably less than about 10% m, typically less than about 5% m, based on the total mass of the mixed solid-liquid blend. In one embodiment of the present invention the dewatered ultra pulverized coal is subjected to a deashing step prior to mixing in the solid-liquid blend product.

A fifth aspect of the present invention provides the use of the mixed solid-liquid blend products described herein in a fractionation process to produce one or more fractionation products.

It will be understood that the present invention may be practiced with further combinations of the disclosed features not explicitly recited above.

The invention is further explained with reference to the accompanying drawings:
1 shows a comparison of the measured percent recovery by mass of the distillate product (solid line) for each sample in Table 4 with that predicted when no volatile components are emitted from coal (dashed line). Shifting the measurements to the left as predicted indicates that additional distillate product was recovered compared to expected.
2 is a graph showing the particle size distribution of exemplary coal sample 7, an Australian high volatility bituminous coal, as determined by laser scattering showing the characteristic size parameters: d50, d90, d95, d98 and d99.

All references cited herein are incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

In one embodiment, the present invention provides a general purpose suitably selected from at least one of “ultrafines” (typical particle size <0.5 mm/500 μm), and “microfines” (typical particle size <20 μm). It is used for blending demineralized (de-ashed), dehydrated (anhydrous) coal particulate material (such as powder), referred to in the industry as “fines” (typical particle size <1.0 mm), with crude oil to produce a blended blended product. it's about The concept includes processes for making fractionated products as well as products made from blended products; It extends in particular to the use of blended products, including products from fractionation by distillation.

Before describing the present invention in more detail, a number of definitions are provided to aid in understanding the present invention.

As used herein, the term “comprising” means that any recited element is necessarily included and other elements may optionally also be included. "Consisting essentially of" means that any recited element must be included, excluding elements that may materially affect the basic and novel characteristics of the enumerated element, and other elements may optionally be included. "Consisting of" means that all elements other than those listed are excluded. Embodiments defined by each of these terms are within the scope of the present invention.

The term “coal” includes, but is not limited to, light coal such as anthracite; bituminous coal; sub-bituminous coal; and solid hydrocarbonaceous material from readily combustible sediment minerals, including lignite (as defined in ISO 11760:2005) comprising subtan.

The term “ash” as used herein refers to the inorganic-such as non-hydrocarbon-mineral component found in most types of fossil fuels, particularly coal. Ash is contained in the solid residue remaining after combustion of coal, sometimes referred to as fly ash. Because of the wide variety of sources and types of coal, the composition and chemistry of the ash vary. However, typical ash content includes several oxides such as silicon dioxide, calcium oxide, iron(III) oxide and aluminum oxide. Depending on its source, the coal further contains trace amounts of one or more substances that may be included in subsequent ash such as arsenic, beryllium, boron, cadmium, chromium, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium. can do.

As used herein, the term “deashed coal” or “low ash coal” refers to coal having a lower proportion of ash-forming components than that in its natural state. As used herein, the related term “demineralized coal” refers to coal having a reduced proportion of inorganic minerals compared to its natural state. The terms "deashed coal" and "demineralized coal" may also be used to mean coal having a low naturally occurring proportion of ash forming components or minerals, respectively.

The term “coal fines” as used herein refers to coal in particulate form having a maximum particle size typically less than 1.0 mm. The term “coal ultrafines” or “ultrafine coal” or “ultrafines” refers to coal having a maximum particle size typically less than 0.5 mm. The term “coal microfines” or “microfine coal” or “microfines” refers to coal having a maximum particle size typically less than 20 μm.

The term "water content" as used herein means the total amount of water in a sample and is expressed as a concentration or mass % (% m). When this term refers to the water content of a coal sample it includes the coal's intrinsic or residual water content and water or moisture absorbed from the environment. As used herein, the term “dehydrated coal” refers to coal having a lower absolute proportion of water than in its native state. The term "dewatered coal" may also be used to refer to coal that has a low proportion of naturally occurring water.

As used herein, the term "crude oil" refers to geologically derived liquid hydrocarbonaceous petroleum. Crude oil may be referred to as unrefined oil. As used herein, the term “refining” means any process that removes impurities or unwanted elements from a material, eg, crude oil. Thus, the term "crude" or "unrefined" in the context of a substance may mean any substance that has not yet been purified, isolated, or further purified to provide a purer substance. The term "crude oil" or "unrefined oil" may relate to oil in the extracted state and is also intended to include oil that has been subjected to water-oil separation and/or gas-oil separation and/or desalting and/or stabilization. will be understood Arabian Heavy, Arabian Light, other Gulf crude oil, Brent, North Sea crude oil, North and West African crude oil, Indonesian, Chinese crude oil and mixtures thereof, but also shale oil, condensate, tar sand Any crude oil, including , gas condensate and bio-based oil, is suitable as raw material for the process of the present invention. Crude oil also includes, but is not limited to, drilling into rock formations; fracking; and/or from a variety of natural sources including oil sand extraction. "Sweet crude oil" is a type of petroleum. The New York Mercantile Exchange has designated petroleum with less than 0.42% m sulfur as sweet petroleum. Petroleum containing high levels of sulfur is referred to as "sour oil".

The term “fractionation” as used herein means the separation of a mixture into different parts. The term "fractionation" shall encompass a separation process in which a specified amount of a mixture (gas, solid, liquid or suspension) is divided into a number of minor fractions (fractions) whose composition varies according to a gradient during a phase transition. Fractionation includes "fractional distillation" in which a mixture is separated into its component fractions or fractions based on differences in their boiling points. The distilled product from the fractionation technique may be referred to as "fractionation product". The viscous residue from atmospheric fractionation can be used as a feedstock for further upgrading via vacuum distillation, as a fuel component, or to contribute to the bituminous fraction. Fractionated or fractionated products have fewer components or are purer than the crude product from which they are derived. Typically, atmospheric distillation of crude oil is completed at or near atmospheric pressure at a temperature in the range of about 300°C to 350°C. The atmospheric residue may then be passed through a vacuum distillation unit operating at around 350° C. with a vacuum of around 40 mmHg (approximately 53 mbar).

The term “dispersion additive” as used herein refers to a substance added to a mixture to facilitate dispersion or to keep particles dispersed in suspension.

The term “hydrocarbon material” as used herein means a material containing hydrocarbons; Hydrocarbons are organic compounds consisting essentially of the elements hydrogen and carbon. The hydrocarbonaceous material may include aromatic hydrocarbons as well as aliphatic hydrocarbons.

Crude oil is an expensive and non-renewable energy source. Coal pulverization is generally considered a waste and is inexpensive and available in sufficient supply. One problem addressed by embodiments of the present invention is to provide an improved feedstock of fractionated fossil fuel derived products. Surprisingly, the provided blended coal-crude product can be subjected to fractional distillation to produce a resulting distillate product that is less expensive than current alternatives but still meets the required product and environmental emission standards. As the amount of crude oil per unit volume in the blend decreases, the method allows users to "stretch" their existing crude oil supply using a low-cost hydrocarbon source that was previously considered a waste by-product of coal mining.

There have been previous studies on how to convert coal into liquid hydrocarbon products. These mainly involve solvent extraction of coal at temperatures above 400° C. under pressure in the presence of hydrogen or a hydrogen donating solvent such as tetralin (1,2,3,4-tetrahydronaphthalene). This has led to several pilot-scale developments and at least one full-scale operational plant using the Shenhua process at Ejin Horo Banner, Ordos, Inner Mongolia, China. However, the development of this process involves very large capital investments and high operating costs.

Traditional coal carbonization and gasification processes, including pyrolysis of coal, can lead to the collection and distillation of coal tar and liquid hydrocarbon products.

It was not previously known that the simultaneous distillation of crude oil and coal fines, particularly coal fines comprising micro and nanoscale coal fines, can provide significant amounts of useful distillate products at temperatures below 400°C. This amount may therefore be due to the presence of coal in addition to these distillate products which may be due to distillation of the crude oil component.

Without wishing to be bound by theory, it is understood that when coal fines are distilled as a blend with crude oil, any coal tar and liquid produced during pyrolysis condense along with the traditional distillate fraction from the crude oil. In addition, the presence of various hydrocarbon species in crude oil that can act as hydrogen donors to facilitate the breakdown of coal polymer structures may enhance the production of condensable hydrocarbons. Existing process equipment for producing these hydrocarbons and pyrolysis tars from coal, namely refinery atmospheric stills and vacuum stills, avoids large investments in major new manufacturing facilities. This represents an important economic advantage of the present invention.

Meanwhile, the present invention encompasses the distillation of crude oil blended with coal fines of any specification to produce a distillate product. Embodiments of the present invention relate to the distillation of crude oil blended with coal fines, wherein the coal fines have specifications, particularly water content and ash, which after distillation provide suitable products and distillate products meeting environmental emission standards for these products. have content. A distillate product that meets or exceeds the required specifications for a product type has a higher value, making the overall process increasingly commercially viable.

Recent developments in coal pulverization treatment allow the use of fine coal products with low water content (<15% m, suitably <3% m) and low ash content (<10% m, suitably <2% m). made it possible The demineralization process also has a beneficial effect on the sulfur content through the removal of pyrite. Demineralization and dewatering of coal fines is typically achieved through a mix of mechanical and thermal dewatering techniques with froth flotation separation specifically designed for ultrafine and fine particles. A typical method for the production of dewatered coal ultrafine powder is provided in US-2015/0184099 which describes a vibration-assisted vacuum dewatering process. However, it will be appreciated that several other suitable dewatering processes also exist in the art, such as, for example, providing coal as a cake comprising coal fine particles in a hydrocarbon carrier from which water has been removed through the use of one or more hydrophilic solvents. There will be.

Any particle size of coal fines suitable for distillation with crude oil is contemplated as being encompassed by the present invention. Suitably, the particle size of the coal fines is in the ultrafine range. Most suitably, the particle size of the coal fines is within the fine range. Specifically, the maximum average particle size may be up to 500 μm. More suitably, the maximum average particle size may be at most 300 μm, 250 μm, 200 μm, 150 μm, or 100 μm. Most suitably, the maximum average particle size may be at most 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, or 5 μm. The minimum average particle size may be 0.01 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, or 5 μm. Accordingly, in certain embodiments, the present invention encompasses the use of nanoscale coal fines having an average particle size in the sub-micron range.

An alternative measure of particle size is to cite a percentage value or “d” value for the ratio of the maximum particle size to the volume of the sample less than that particle size. In the present invention, any particle size of coal fines suitable for distillation with crude oil is considered to be encompassed by the present invention. Suitably, the particle size of the coal fines is in the ultrafine range. Most suitably, the particle size of the coal fines is within the fine range. Specifically, the maximum particle size may be up to 500 μm. More suitably, the maximum particle size may be at most 300 μm, 250 μm, 200 μm, 150 μm, or 100 μm. Most suitably, the maximum particle size may be up to 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, or 5 μm. The minimum particle size may be 0.01 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, or 5 μm. Any “d” value can be associated with these particle sizes. Suitably, the “d” value associated with any of the above maximum particle sizes may be d99, d98, d95, d90, d80, d70, d60, or d50.

In accordance with certain embodiments of the present invention, a method is provided for blending (ie suspending) the solid particulate material of dehydrated, demineralized fine coal in crude oil prior to fractionation. Fractionation at near or slightly above atmospheric pressure, followed by fractionation at reduced pressure, of valuable low distillate products (naphtha: boiling range 85-177°C, kerosene: boiling range 177-232°C and diesel: boiling range 232-343 ℃) is produced in an amount significantly higher than the amount accounted for by distilling only crude oil components. These low distillate products therefore result from the presence of fine and/or ultrafine coal.

Accordingly, in accordance with certain embodiments of the present invention, described in greater detail below, the crude oil/fine coal dispersion is pumped through a desalting and preheating process unit at ambient or elevated temperature and subsequently to a fractionation column, typically at or near atmospheric pressure. . The resulting residue from the atmospheric distillation step is then transferred to a vacuum distillation plant and fractionated further. The distillate fraction in both atmospheric and vacuum distillation processes is used as a blend component for the final oil product or as a feed to other refinery processing units such as catalytic crackers, hydrocrackers, thermal crackers, visbreakers, etc. can be used The vacuum residue may also be further processed by oil refining processing units such as cokers, visbreakers, etc. or used for bitumen/asphalt production.

The technology upgrades coal pulverization, previously considered a waste by-product of mining. The total cost of crude oil decreases as does the amount of crude oil per unit of distillate product.

The amount of fine coal that can be blended with crude oil is at least 1% m (1% by mass), suitably at least 5%m, typically around 10%m, at most 70%m, suitably at most 60%m; Optionally up to 50% m.

The invention is further illustrated by the following non-limiting examples.

Example

Example 1a - Demineralization and dewatering of coal fines can be achieved through a mixture of mechanical and thermal dewatering techniques with froth flotation separation designed specifically for ultrafine and fine particles.

The coal slurry is screened, collected in a tank, and froth flotation is added using a controlled dose rate. A fine particle separator filled with process water and filtered air from an enclosed air compressor is used to separate hydrophobic carbon materials from hydrophilic mineral materials. Foam containing carbon particles overflows the tank and the foam collects in an open top gutter. The mineral pulp is held in a separation tank until discharged, while the demineralized coal slurry is degassed before being pumped to the pelletizing stage. Further coal particle size reduction can be achieved by a variety of known milling techniques, including, if desired, the use of hydrocarbon oils as milling aids.

Mechanical dewatering of the demineralized fine coal slurry is done through a filter press or tube press. Suitable equipment is manufactured by Metso Corporation, Fabianinkatu 9 A, PO Box 1220, Helsinki, FIN-00101, FIN-00130, Finland. The resulting fine coal wet cake is either thermally dried in powder form (suitable equipment is manufactured by GEA Group Aktiengesellschaft, Peter-Müller-Strasse 12, Düsseldorf, Germany 40468) or pellets prior to drying. can get angry For pelletization, certain modifiers can be added to the filter cake in a mixer to optimize pelletization and sent to an extruder where the modified cake is compressed into pellets. The demineralized coal pellets are then transported to a pellet dryer where deoxygenated hot process air is blown directly over the fine coal pellets and dried by heat. Suitable equipment is manufactured by STELA Laxhuber GmbH, D-84323 Mashing, Ottingerstrasse 2, Germany.

Example 1b - Grinding Larger Lumps and Grains of Coal in Wetting Medium to Obtain Coal Microfines

The type of coal may be selected based on advantageous properties of the coal, such as low ash or water content or ease of grindability (eg, high Hardgrove grindability Index) or reactivity. Microfines were obtained by various standard crushing and grinding size reduction techniques in a wet medium followed by dewatering.

1. Crush the produced washed wet coal (eg Coal D or Coal F, Table 3) to reduce it to approximately 6 mm at or near 50 mm, eg via a high pressure grinding roller mill or jaw crusher: suitable equipment is manufactured by Mecho Corporation or FLSmidth of 77 Bigerslev Ale, DK-2500 Balvi, Copenhagen, Denmark.

2. Produce a wet <6 mm slurry and reduce to 40 μm using a suitable ball mill, rod mill or stirred media detritor: suitable equipment is manufactured by Mecho Corporation.

3. Using a nanomill, reduce the <40μm slurry to <1μm or less, suitably using a peg mill, a horizontal disk mill or a vertically agitated media detriter: suitable equipment is Germany, 95100 Shelb, Sedanstra NETZSCH-Feinmahltechnik GMBH in SE 70, or manufactured by Mecho Corporation, IsaMill ^TM can also be used to reduce particle size to <5 μm or less by abrasion and abrasion: QLD 4000, 160 Ann Street, Brisbane, Australia, Level 10 Material, Glencore Technology.

4. Dewatering from approximately 50% m to <20% m with a tube press operating at high pressure through a membrane or vertical plate pressure filter: suitable equipment is manufactured by Mecho Corporation. Alternative dewatering methods include filter presses such as those of Andritz AG, Stätger Strasse 18, Graz, 8045, Austria.

5. Dehydration to <2% m by:

a. Thermal drying such as fluidized bed, rotary, flash or belt dryers: suitable equipment is the GEA Group Aktiengesselschaft, Peter-Müller-Strasse 12, Düsseldorf, Germany 40468, and 84323 Mashing, Laxhuberplatz 1, Germany. It is manufactured by the same company as Stella Laxchver GmbH.

b. Solvent-dehydration techniques with alcohols, ethers or ketones as described, for example, in US-3327402, US-4459762 and US-7537700.

Example 1c - Grinding Larger Lumps and Grains of Coal in the Dry State to Obtain Coal Microfines

Coal microfines were obtained in the dry state by standard grinding, grinding and fine grinding size reduction techniques.

1. Crush the dry raw coal bed using a jaw crusher to a size of <30mm.

2. Using a ball mill with classifier or centrifugal attrition mill to pulverize the dried coal to a size of <30mm to <45μm; Suitable equipment includes: Loesche GmbH, 243 Hansaallee, Düsseldorf, Germany 40549; CV6 5RE, UK; Attritor Limited, 12 The Stampings, Coventry Blue Ribbon Park, West Midlands. ) is manufactured by

3. Reduction to a particle size of <1 μm with an air micronizer (or jet mill): suitable equipment is British Rema Process British Rema Process, Foxwood Close, Chesterfield, UK S41 9RN Equipment Ltd).

Example 1d - Grinding of dry coal to fuel oil or similar oil product to obtain a fine coal-fuel oil cake

Grinding of dry coal with crude oil or related petroleum products as a fluid medium (see Example 1b above) in a Netzsch Laboratory Agitator Bead Mill apparatus or Metso Stirred Media Detritor A cake of fine coal in crude oil is obtained.

The particle size distribution is typically determined by laser scattering, which measures the particle volume of a particle between a series of incremental size ranges. Figure 2 shows the particle size distribution of Coal 7 (shown in Table 3 below). When the particle size is greater than 63 μm, it is practically possible to separate the coal into fractions of different sizes by sieving, and coal sample 6 is prepared between two sieve sizes 63 μm and 125 μm, Table 3.

Typically the particle distribution width is quantified by the particle diameter values d50, d90, d95, d98 and d99 on the x-axis as shown in FIG. 2 . d50 is defined as the diameter at which half of the population falls below this value. Similarly, 90% of the distribution is below d90, 95% of the population is below d95, 98% of the population is below d98, and 99% of the population is below the d99 value.

Example 2a - Suspension of fine coal in crude oil can be achieved through high shear mixing of various types of fine coal.

Fine coal mixed with hydrocarbon oil in the form of dried fine coal powder, pellets or cake of dried fine coal is deagglomerated and dispersed in crude oil using a high shear mixer in a vessel. If necessary, dispersing additives are included in the blend to ensure sufficient storage stability. Optionally, the vessel may be equipped with ultrasonic capability to induce cavitation to enhance deagglomeration. Shear mixing is done at room temperature or at elevated temperatures, typically up to 50° C. for more viscous crude oils. Suitable shear mixers include Charles Ross & Son Co., 710 Old Willets Path, Hauppauge, NY 11788, 11788, NY and 01028, East Long Meadows, MA, USA. , 355 Chestnut St. (East Longmeadow, MA 01028, USA), by Silverson Machines Inc. The process typically takes place in a distillation plant, and the resulting crude oil/fine coal dispersion can be stored in tanks for a short period of time or immediately transferred to a distillation plant typically equipped in an oil refinery.

Example 2b - Suspension of fine coal in crude oil can be achieved by injecting coal fines directly into a crude oil stream or by injecting coal fines directly into a distillation chamber.

The dried fine coal powder is obtained by drying a wet cake of fine coal particles produced by mechanical drying of froth flotation coal fines, by crushing and grinding dried pellets of fine coal, or by forming the underlying ash coal bed. It can be induced by crushing and grinding. This dried fine coal powder is typically prepared in a crude oil preheating process in a stream of carrier gas (typically nitrogen, air or oxygen depleted air or mixtures thereof) prior to introduction of the crude oil stream into the fractionation column at or near atmospheric pressure. It is fed into a unit (typically 120-150°C), an electrostatic desalination unit or a final heating process or furnace unit (280-400°C, typically 340-370°C). Alternatively, the dried fine coal powder thus prepared may be directly injected at the bottom of the fractionation column.

Example 3 - Fractionation of North Sea Crude A and West Virginia Fine Coal 1 Blend Using Standard Small Scale (200 mL) Distillation Unit Process and Procedures

The crude/fine coal dispersion is pumped at ambient or high temperature through a desalting and preheating process unit and then pumped to a fractionation column, typically at atmospheric pressure. Thereafter, the residue produced in the atmospheric distillation step is transferred to a vacuum distillation plant and further fractionated.

A typical light, sweet North Sea crude A (properties provided in Table 1) was blended with West Virginia low volatility bituminous coal 1 (properties provided in Table 3), USA and a series of analytical test results were obtained for various important parameters, see Table 2. Addition of 5%m coal 1 to crude A surprisingly only slightly increased density (0.833 to 0.837g/ml @15°C), viscosity (5.1 to 5.5cSt @50°C) and sulfur content (0.241% to 0.255%m). resulted in

Analytical and Distillation Characteristics of Tested Crude Oils crude oil code distillate fraction Temp, C A B C D Density @ 15℃ kg/m ³ 833 805 870 912 Kinematic Viscosity @ 20℃ mm ² /s 5.1 2.2 22.1 85 Carbon Residue (MCRT) %m/m 1.2 0.6 4.4 1.9 sediment by hot filtration %m/m <0.01 0.01 0.01 0.01 Pour point ℃ ℃ -18 -15 -30 -54 computerist mgKOH/g 0.09 0.05 0.09 3.2 ash %m/m <0.001 0.001 0.01 0 sulfur %m/m 0.24 0.18 1.7 0.4 Distillation result 200mL 15L 200mL volume volume condensate n.a. 2.4 n.a. low boiling ingredients <85 5.0 7.4 8.0 4.6 0 naphtha 85-177 23.5 23.5 37.0 15.2 2.1 Kero 177-232 11.1 10.3 11.2 9.8 5.7 diesel 232-343 21.1 21.3 21.6 19.2 28.3 LVGO 343-427 13.8 12.0 9.6 14.1 21.7 HVGO 427-550 15.0 14.5 6.6 17.0 27.7 vacuum residue >550 10.5 8.4 6.0 20.0 14.5 final boiling point ℃ 607 517 542 559

Surprisingly the carbon residue increased much less than expected: only 0.55%m from 1.19%m of crude A to 1.74%m of the 5% blend, Table 2. Coal 1 was 80.2%m (with 100%-volatile content) calculated) of mixed non-volatiles content (fixed carbon + ash content). The nonvolatile content provides a measure of the amount of carbon and ash content expected to remain after distillation. Based on these values for the carbon residue of crude A with 5% m of coal 1, the addition of 5% of coal 1 is expected to increase the carbon residue by approximately 4% m. However, the observed carbon residue increase is very small (0.55% m), indicating that the fine coals produce significantly more volatiles (gas and liquid products) when mixed with crude oil than when heated alone in proximity analysis.

Analysis of Coal-Crude Oil Blends 5% coal in crude A 1 distillate fraction Temp, C Density @ 15℃ kg/m ³ 837 Kinematic Viscosity @ 20℃ mm ² /s 5.5 Carbon Residue (MCRT) % m/m 1.74 sediment by hot filtration %m/m 0.74 Pour point ℃ ℃ -9 computerist mgKOH/g 0.09 ash %m/m 0.19 sulfur %m/m 0.26

The distillation properties for the lowest boiling 50%v from Crude Oil A and blends of Crude A and Fine Coal 1 were determined according to ASTM D86 Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure. Using 200 mL samples in a laboratory batch manual distillation unit, the boiling range properties of the oil product were quantitatively determined under conditions designed to provide approximately one theoretical plate fractionation. Periodic systematic readings of temperature readings and condensate volumes were made until the cumulative volume of liquid distillate fractions reached 50%v, which in these crystals corresponded to distillation temperatures between 270°C and 280°C.

Distillation properties for 50%v residue from atmospheric manual distillation of crude A, and a blend of fine coal 1 and crude A, were determined according to ASTM D1160 Standard Test Method for Distillation of Petroleum Products at Reduced Pressure. This test method covers the measurement at reduced pressure for the boiling point range of petroleum products that can be partially or fully vaporized at a maximum liquid temperature of 400°C. Samples are distilled at precisely controlled pressures between 0.13 kPa and 6.7 kPa (1 mm and 50 mm Hg) under conditions designed to provide approximately one theoretical plate fractionation. Data are prepared from which distillation curves relating to final boiling point and % distilled volume and atmospheric equivalent boiling point temperature are obtained.

Table 4 shows the volume (X) of the distillate fraction thus obtained for crude oil “A” and for a blend of coal 1 at concentrations of 5%m, 7.5%m and 10%m in crude oil “A” . Boiling point ranges for low boiling constituents, naphtha, kerosene (kero), diesel, light vacuum gas oil (LVGO) and heavy vacuum gas oil (HVGO), as defined by the US Energy Information Administration, are in degrees Fahrenheit (°C). F) to Celsius (°C).

The volumes of these distillate fractions are based on the observed volume (X): 95%m crude oil: 5%m inert blend (and 92.5%m crude oil and 7.5%m inert, respectively; 90%m crude oil and 10%m inert, respectively) material) was calculated (Y), see Table 4. It also represents the volume difference (X-Y) between the observed volume (X) and the calculated volume (Y) for the inert solid material. Therefore, the value of (X-Y) is a measure of the effect of fine coal on the distillation properties of crude oil. A positive value (in bold) indicates that the increase in the yield of that fraction is due to the presence of fine coal; A negative value (indicated in italics) indicates that a reduction in yield of the fraction has occurred.

Surprisingly, the low-boiling distillates (naphtha, kerosene and diesel) consistently provided higher than expected yields. Likewise surprisingly the heavy gas oil distillate fraction expected to contain any resulting coal pyrolysis liquid provided lower than expected yields. The yield of light vacuum gas oil was higher in the 5%m fine coal blend, but decreased with decreasing yields in the equivalent 7.5%m and 10%m blends. The yield change of each of these five fractions gradually increased or decreased as the fine coal ratio increased from 0% to 5%m, 7.5%m, and 10%m. In this case the total volume of additional distillate was increased to 4.7%, 5.8% and 5.8% respectively for the 5%m, 7.5%m and 10%m blends, respectively. Mainly increased distillates were found in naphtha, kero and diesel fractions.

By correcting for ash content, calculate the %m of organic coal converted to all distillates, distillates <427°C (ie, excluding heavy vacuum gas oils) and distillates <343°C (excluding both light and heavy gas oil fractions) did A surprisingly high conversion (49%-104% volume of distillate per unit mass of coal, %v/m) was achieved, and it is evident that a large proportion of fine coal 1 was converted to distillate product in the presence of crude oil A.

The differential yield of the vacuum residue increased as expected with an increase in the proportion of fine coal 1 .

Example 4 Fractionation of a blend of West Virginia Fine Coal and Different Crude Oils of Different Fine Particle Sizes can be performed using standard distillation unit processes and procedures.

The distillation properties of crude oils A, C and D and blends of these crudes and fine coals 1, 2 and 3 were measured under atmospheric pressure and reduced pressure according to the procedure described in Example 3.

Crude A is a typical light, sweet North Sea crude with low sulfur content producing higher yields of lighter distillates, naphtha and diesel. Crude C is a medium density sweet crude and also originates from the North Sea but produces high yields of heavy fractions: diesel and vacuum gas oils. Crude oil D is a sulfur-rich, medium-density sour Russian crude oil, which also produces mainly a heavier distillate. Table 1 provides analytical and distillation characteristics for these crude oils.

These crude oils were blended with West Virginia Low Volatility Bituminous Coal 1, 2 and 3 at different concentrations up to 20% m. Coal 1, 2, and 3 have different grain size characteristics, so that Table 3, Coal 3 is the most finely ground with 98% particles <10 μm in diameter and a d50 of 1.8 μm (ie 50% of the particles are less than 1.8 μm). did it Coal 1 and Coal 2 have relatively similar d50 values of 4.5 μm and 5.8 μm, respectively, but Coal 1 has a significantly higher content of 8.5% compared to 2.7% of Coal 2. No systematic differences were observed for coal conversion between coals 1, 2, and 3, suggesting that the discrimination of coal grain size within micro-level limits is not a significant determinant.

As in Example 3, significant volumes of distillate due to fine coal were obtained for all blends shown in Table 5 with increases ranging from 2.3%v to 7.6%v. Again increased distillate was found mainly in naphtha, kero and diesel fractions. Even at a high concentration blend of 20% m coal 2 of crude A, a coal conversion yield of 34% v/m was obtained for distillate <427° C. (ie excluding heavy vacuum gas oil).

Significant coal conversion was also observed with the blend of Crude Oils C and D with Coal 2. For example, a conversion yield of 39% v/m to all distillate was obtained from crude C with 15% coal 2, and a coal conversion yield of 71% v/m was obtained with a blend of 5% coal 2 in Russian crude D. Obtained for a distillate <343°C.

It is noteworthy that the final boiling temperature (FBT) tends to decrease with increasing coal concentration, Table 5. This reduces the amount of heavy gas oil that can be collected with the vacuum distillation unit. Therefore, FBP is continuously lowered from 607°C to 550°C, 516°C, and 479°C as the concentration of coal 2 in crude oil A increases from 0% to 10%m, 15%m, and 20%m, respectively. FBP is a measure of the onset of cracking of heavier crude oil components, and further distillation is limited as the evolution of gas reduces the applied vacuum. Yields of vacuum gas oil in full-scale distillation plants are expected to be higher because there is a large difference (typically 50-100° C.) between the temperature at which the distillation takes place over the heated vessel and the temperature within the heated vessel itself in the small laboratory setup. Thus, cracking in laboratory setups occurs earlier than would be expected in full-scale plant stills.

Example 5 Fractionation of blends of different crude oils and coals of variously different grades, origins, particle sizes and mineral content can be performed using standard distillation unit processes and procedures.

The distillation properties for North Sea Crude Oils A and B, and ten coal samples 4-13 and blends of these crudes were determined under atmospheric pressure and reduced pressure according to the procedure described in Example 3, see Table 6.

Crude B, like Crude A, is a light, sweet North Sea crude with low sulfur content, but produces a higher yield of light distillate, naphtha, see Table 1.

These crude oils were distilled into highly volatile bituminous coals 4-9 from the United States, Colombia and Australia representing the Carboniferous, Paleocene and Permian sedimentary epochs, respectively. Crude A was also tested with 10% addition of medium volatile bituminous coal from the Czech Republic and Mongolia plus sub-bituminous coal and lignite (atan) from Mongolia. The latter two coals extend the geological epochs included in the Jurassic and Cretaceous.

Coal 10-13 increases the range of tested coal mineral matter content (estimated as ash content). Coal 3-9 all have an ash content of less than 2% m d.b. on a dry basis. Coal 2 is 2% m, d.b. and 3% m, d.b. has an ash content of less than Coal 1, 10, 12, and 13 were 4% m, d.b. to 9% m, d.b. range of ash content, while the ash content of coal 11 is 15% m, d.b. it is excess

Although a wide range of coal grades and ash contents were covered by coal 10-14, significant %volume (%v/m) of distillate per unit mass of coal conversion of organic coal was observed in the following ranges: -

15-52% v/m for all distillates,

33-58% v/m for distillate <427°C,

-75% v/m for distillate <343°C (note that lignite with high intrinsic moisture and high oxygen content produces generally high volumes of low-boiling components which may contain significant amounts of water do).

Coal 5 and 7 are fine coals with particle sizes similar to those of Coal 1-3 used in Examples 3 and 4 (d50 of 4.0 μm and 3.2 μm, respectively). Coal 11, 9 and 10 are coarser in size with d50s of 8.2 μm, 9.4 μm and 10 μm, respectively, while coals 4, 7, 12 and 13 are more coarse with d50 in the range of 13-18 μm. Coal 6 was made with a sieve between 63 μm and 125 μm and contained the largest particle size tested. As coal particle size increases, co-distillation with crude oil becomes more problematic, but not insoluble. The coarser coal samples 4 and 7 and vacuum distillation of crude oil were less stable and more difficult to control. In addition, the dispersion of 63-125 μm coal 6 in crude oil B was decomposed after 30 minutes and started to affect the smooth operation of atmospheric distillation. Despite these operational differences, significant % conversion of organic coal was still observed in the following ranges:-

Note that 3-55% v/m for all distillates (conversion values less than 30% reduce usable heavy gas oil, consistent with a lower final boiling point (FBP) possibly due to early onset of cracking) );

21-66% v/m for distillate <427°C;

· 22-83% v/m for distillate <343°C.

As in the previous examples, significant volumes of distillate attributable to fine coal were obtained for all blends shown in Table 6 with increases ranging from 1.9%v to 5.3%v (these blends affected by early cracking). excluding). Again increased distillate was found mainly in naphtha, kero and diesel fractions. Tests 15 and 20 show lower % coal conversion levels (3%v/m and 5%v/m, respectively) than the other tests. This is probably due to the low FBP (early onset of cracking) in both cases leading to the low yield of HVGO, which is higher than the usual differential temperature between the heating vessel and the distillation temperature in this experimental setup.

Example 6 - Larger scale (15L) fractionation of a blend of North Sea Crude A and West Virginia Fine Coal 2 can be performed using standard large scale distillation unit processes and procedures.

Distillation properties for the lowest boiling fraction from a blend of crude A, and fine coal 2 (5%m, 10%m, and 15%m) with crude A, ASTM D2892- for the distillation of crude petroleum using a 15L sample. It was determined according to 16 standard test methods (15 theoretical plate columns). This test method determines its value as one of many tests on crude oil. It provides estimates of the yields of fractions of different boiling ranges and is therefore valuable in technical discussions of its commercial nature. Together with the relevant analysis of the fractions collected (see Example 7), this distillation approach is commonly referred to as a crude oil assay and is used as an industry approach to assess the suitability of crude oils and their value to oil refiners.

The residue from the atmospheric distillation was transferred to another distillation flask and reevaporated under low vacuum according to ASTM D5236-13 Standard Test Method for Distillation of Heavy Hydrocarbon Mixtures (Vacuum Postile Method). The maximum achievable atmospheric equivalent temperature (AET) can be as high as 565° C., but depends on the heat resistance of the charge; AETs were achieved between 540° C. and 555° C. for the Crude A and Coal 2-Crude A blends. The sample is distilled at precisely controlled pressure within the range of 0.1-0.2 mmHg.

Approximately 30 individual distillation cut samples were collected over a continuous temperature range from atmospheric and vacuum distillation mixing procedures and the yield of each cut was determined. Distillation cuts were mixed to correspond to each distillate fraction temperature range (eg kero) to prepare samples for further analysis and yielded for each distillate Crude A, 5% Coal 2-Crude A and 10% Calculated for Coal 2-Crude A Blend, Table 7.

Significant %v/m conversion of organic coal was observed for 5%, 10% and 15% blends of Crude A and Coal 2 in the following ranges:-

31-52% v/m for distillate <427° C.,

· 28-35% v/m for distillate <343°C.

Increased distillates were found mainly in the low boiling component, diesel and light vacuum gas oil fractions. The yield data for heavy gas oils are unreliable as the longer residence time in this laboratory setup causes early onset of cracking, as in the 200 mL small scale test.

Example 7 - Distillate Fraction Made by Larger Scale (15L) Fractionation of North Sea Crude A and West Virginia Fine Coal 2 Blends Has Properties Very Similar to Equivalent Fractions Derived from Crude Oil A

Many of the properties determined for the distillate fraction from the large-scale distillation of a coal 2-crude A blend show a constant small trend as the coal concentration increases from 0% to 5% and 10%, see Table 8. All these property changes are directional as expected based on knowledge of the properties of Crude A and Coal 2 (eg, the coal structure typically contains higher aromatics and higher molecular weight units than Crude Oil), and Coal 2 is was confirmed to be the origin of some of the Moreover, these changes are small and will not degrade the quality of the resulting distillate fraction to a significant extent. So as the coal 2 concentration increases:-

· Increased density for light naphtha, light vacuum gas oil and heavy vacuum gas oil fractions;

· increased viscosity for LVGO and HVGO fractions;

· Slight increase in sulfur content for light naphtha, heavy naphtha, LVGO and HVGO;

· Copper corrosion to light naphtha and heavy naphtha is improved;

· Increased aromatics content for light naphtha, heavy naphtha, Kero and diesel.

While specific embodiments of the invention have been disclosed in detail herein, they have been made by way of illustration and description only. The foregoing embodiments are not intended to limit the scope of the present invention. The inventors contemplate that various substitutions, changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention.

Claims (35)

The pulverized coal products are:
a. a water content of less than 3% by mass, based on the total mass of the coal product;
b. an ash content of less than 2% by mass, based on the total mass of the coal product; and
wherein the coal product comprises hydrocarbonaceous particles, wherein at least 95% by volume (%v) of the particles have a diameter of 100 μm (microns) or less;
at least 50% by volume (%v) of said hydrocarbonaceous particles have a diameter of 50 μm (microns) or less,
wherein said hydrocarbonaceous particles have an average particle size of at most 10 μm in diameter,
The hydrocarbonaceous particles are from hard coal, microfine coal, anthracite, bituminous coal, sub-bituminous coal, brown coal, or a combination thereof. A pulverized coal product comprising a selected sedimentary mineral-derived solid hydrocarbonaceous material. The pulverized coal product according to claim 1 , wherein the water content is less than 2% by mass, based on the total mass of the coal product. The pulverized coal product according to claim 1 , wherein the ash content is less than 1% by mass based on the total mass of the coal product. The pulverized coal product of claim 1 , wherein at least 50% by volume (%v) of the particles have a diameter of 30 μm (microns) or less. The pulverized coal product of claim 1 , wherein at least 50% by volume (%v) of the particles have a diameter of 20 μm (microns) or less. The pulverized coal product according to any one of claims 1 to 5, wherein the pulverized coal product is in the form of pellets. Pellets comprising the pulverized coal product according to claim 1 . A process for producing the pulverized coal product according to any one of claims 1 to 5, wherein the process comprises the steps of:
a. providing a coal feedstock;
b. froth flotation of coal feedstock;
c. collecting the flotation coal product; and
d. dewatering the flotation coal product;
A process for providing a pulverized coal product comprising: The method of claim 8 , wherein the coal feedstock is pre-ground to provide the required particle size. 10. The method of claim 9, wherein the pre-grinding step comprises a ball mill, a centrifugal attrition mill, a rod mill, a bead mill, a peg mill, a horizontal A method of manufacturing, carried out using a horizontal disc mill or stirred media detritor. The process according to claim 8 , wherein the flotation coal product is milled to further reduce particle size prior to dewatering in step (d). The process according to claim 8 , wherein the dehydration is via mechanical, solvent and/or thermal dehydration. 13. The method of claim 12, wherein the thermal dehydration is via a fluidized bed, rotary, flash or belt dryers, the solvent dewatering is performed with an alcohol, ether or ketone and the mechanical dewatering is performed with a filter press ( A method of manufacturing, carried out through a filter press) or a tube press. The process according to claim 8 , wherein the flotation coal product is compressed into pellets prior to dewatering in step (d). The process according to claim 14 , wherein the pellets are dewatered by blowing hot air deoxygenated in step (d) over the pellets. A process for producing the pulverized coal product according to any one of claims 1 to 5, wherein the process comprises the steps of:
a. providing a coal feedstock having a low ash content of <5% by mass m;
b. crushing the coal feedstock to reduce the particle size to 6 mm;
c. reducing the particle size of the coal feedstock to provide a reduced particle size coal feedstock having a particle size of 40 microns; and
d. dewatering the reduced particle size coal feedstock;
A process for providing a pulverized coal product comprising: The method of claim 16 , wherein the coal feedstock is crushed in step (b) using a high pressure grinding roller mill or a jaw crusher. 17. The method of claim 16, wherein the coal feedstock is a ball mill, a centrifugal attrition mill, a rod mill, a bead mill, a peg mill in step (c). mill), a horizontal disc mill or stirred media detritor, an air microniser or a jet mill to reduce particle size. The method of claim 18 , wherein the ball mill is with or without a classifier. The method of claim 16 , wherein the dewatering is via mechanical and/or thermal dehydration. 21. The method of claim 20, wherein thermal dehydration is via fluidized bed, rotary, flash or belt dryers, solvent dewatering with alcohol, ether or ketone and mechanical dewatering with a filter press ( A method of manufacturing, carried out through a filter press) or a tube press. The method of claim 16 , wherein the reduced particle size coal feedstock is compacted into pellets prior to dewatering in step (d). 23. The process according to claim 22, wherein the pellets are dewatered by blowing hot air deoxygenated in step (d) over the pellets. delete delete delete delete delete delete delete delete delete delete delete delete

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